US6476080B2 - Blowing agent compositions containing hydrofluorocarbons and a low-boiling alcohol and/or low-boiling carbonyl compound - Google Patents
Blowing agent compositions containing hydrofluorocarbons and a low-boiling alcohol and/or low-boiling carbonyl compound Download PDFInfo
- Publication number
- US6476080B2 US6476080B2 US09/999,277 US99927701A US6476080B2 US 6476080 B2 US6476080 B2 US 6476080B2 US 99927701 A US99927701 A US 99927701A US 6476080 B2 US6476080 B2 US 6476080B2
- Authority
- US
- United States
- Prior art keywords
- blowing agent
- hfc
- composition
- low
- boiling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 130
- 239000004604 Blowing Agent Substances 0.000 title claims abstract description 127
- 238000009835 boiling Methods 0.000 title claims abstract description 50
- 150000001728 carbonyl compounds Chemical class 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 43
- 150000001298 alcohols Chemical class 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 35
- 239000001569 carbon dioxide Substances 0.000 claims description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 27
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 abstract description 91
- 229920000642 polymer Polymers 0.000 abstract description 59
- 238000000034 method Methods 0.000 abstract description 15
- 239000004793 Polystyrene Substances 0.000 description 31
- 229920002223 polystyrene Polymers 0.000 description 30
- 238000012005 ligant binding assay Methods 0.000 description 23
- 238000005187 foaming Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- -1 aliphatic alcohols Chemical class 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 3
- 210000000497 foam cell Anatomy 0.000 description 3
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 2
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 2
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 2
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- ROVMKEZVKFJNBD-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,5,5,5-undecafluoro-4-(trifluoromethyl)pentane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)C(F)(F)F ROVMKEZVKFJNBD-UHFFFAOYSA-N 0.000 description 1
- MPEFSWGYIJNMCW-UHFFFAOYSA-N 1,1,1,2,2,3,4,4,4-nonafluoro-3-(trifluoromethyl)butane Chemical compound FC(F)(F)C(F)(F)C(F)(C(F)(F)F)C(F)(F)F MPEFSWGYIJNMCW-UHFFFAOYSA-N 0.000 description 1
- NBQYGIPVNCVJJP-UHFFFAOYSA-N 1,1,1,2,3,4,4,4-octafluoro-2,3-bis(trifluoromethyl)butane Chemical compound FC(F)(F)C(F)(C(F)(F)F)C(F)(C(F)(F)F)C(F)(F)F NBQYGIPVNCVJJP-UHFFFAOYSA-N 0.000 description 1
- KDWQLICBSFIDRM-UHFFFAOYSA-N 1,1,1-trifluoropropane Chemical compound CCC(F)(F)F KDWQLICBSFIDRM-UHFFFAOYSA-N 0.000 description 1
- RKIMETXDACNTIE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorocyclohexane Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F RKIMETXDACNTIE-UHFFFAOYSA-N 0.000 description 1
- SEEJHICDPXGSRQ-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6-undecafluoro-6-(1,1,2,2,2-pentafluoroethyl)cyclohexane Chemical compound FC(F)(F)C(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F SEEJHICDPXGSRQ-UHFFFAOYSA-N 0.000 description 1
- SOJZMJXWEOBDIC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5-nonafluorocyclopentane Chemical compound FC1C(F)(F)C(F)(F)C(F)(F)C1(F)F SOJZMJXWEOBDIC-UHFFFAOYSA-N 0.000 description 1
- RBTROQHBNLSUTL-UHFFFAOYSA-N 1,1,2,2,3,4-hexafluoro-3,4-bis(trifluoromethyl)cyclobutane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C1(F)C(F)(F)F RBTROQHBNLSUTL-UHFFFAOYSA-N 0.000 description 1
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 1
- SOZFIIXUNAKEJP-UHFFFAOYSA-N 1,2,3,4-tetrafluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1F SOZFIIXUNAKEJP-UHFFFAOYSA-N 0.000 description 1
- UHHYOKRQTQBKSB-UHFFFAOYSA-N 1,2,3,5-tetrafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1 UHHYOKRQTQBKSB-UHFFFAOYSA-N 0.000 description 1
- SDXUIOOHCIQXRP-UHFFFAOYSA-N 1,2,4,5-tetrafluorobenzene Chemical compound FC1=CC(F)=C(F)C=C1F SDXUIOOHCIQXRP-UHFFFAOYSA-N 0.000 description 1
- JXUKFFRPLNTYIV-UHFFFAOYSA-N 1,3,5-trifluorobenzene Chemical compound FC1=CC(F)=CC(F)=C1 JXUKFFRPLNTYIV-UHFFFAOYSA-N 0.000 description 1
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 1
- QUGUFLJIAFISSW-UHFFFAOYSA-N 1,4-difluorobenzene Chemical compound FC1=CC=C(F)C=C1 QUGUFLJIAFISSW-UHFFFAOYSA-N 0.000 description 1
- FCBJLBCGHCTPAQ-UHFFFAOYSA-N 1-fluorobutane Chemical compound CCCCF FCBJLBCGHCTPAQ-UHFFFAOYSA-N 0.000 description 1
- OFERIJCSHDJMSA-UHFFFAOYSA-N 1-fluorohexane Chemical compound CCCCCCF OFERIJCSHDJMSA-UHFFFAOYSA-N 0.000 description 1
- UTPYTEWRMXITIN-YDWXAUTNSA-N 1-methyl-3-[(e)-[(3e)-3-(methylcarbamothioylhydrazinylidene)butan-2-ylidene]amino]thiourea Chemical compound CNC(=S)N\N=C(/C)\C(\C)=N\NC(=S)NC UTPYTEWRMXITIN-YDWXAUTNSA-N 0.000 description 1
- YZXSQDNPKVBDOG-UHFFFAOYSA-N 2,2-difluoropropane Chemical compound CC(C)(F)F YZXSQDNPKVBDOG-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 235000019534 high fructose corn syrup Nutrition 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- LOQGSOTUHASIHI-UHFFFAOYSA-N perfluoro-1,3-dimethylcyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)C1(F)F LOQGSOTUHASIHI-UHFFFAOYSA-N 0.000 description 1
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/127—Mixtures of organic and inorganic blowing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
Definitions
- the present invention relates to a blowing agent composition containing a hydrofluorocarbon (HFC) having a boiling point of 30° C. or higher and lower than about 120° C. (mid-range low-boiling HFC), a HFC having a boiling point lower than 30° C. (low-range low-boiling HFC), and at least one component selected from low-boiling alcohols and low-boiling carbonyl compounds.
- HFC hydrofluorocarbon
- HFC hydrofluorocarbon
- low-range low-boiling HFC low-range low-boiling HFC
- the present invention further relates to polymeric foams and the use of such a blowing agent composition to produce polymeric foams, and foamable polymer compositions comprising a polymer that has such blowing agent compositions dispersed therein.
- alcohols have drawbacks when used as blowing agents.
- An alcohol can react with halogenated components that are present in the foam, such as halogenated flame retardants, to produce a corrosive acid.
- the acid tends to corrode metal equipment.
- alcohols can escape into the atmosphere whereby they contribute undesirably to volatile organic compound (VOC) emissions.
- VOC volatile organic compound
- Low-boiling carbonyl compounds such as ketones and aldehydes
- LBC Low-boiling carbonyl compound
- VOC volatile organic compound
- Blowing agents comprising HFCs are gaining popularity as regulations encourage replacing hydrochlorofluorocarbon (HCFC) and chlorofluorocarbon (CFC) blowing agent components, both of which can contribute to ozone depletion.
- HFCs have a thermal conductivity lower than most polymers or blowing agents (other than HCFCs and CFCs) so HFC residuals in a polymeric foam can lower the foam's thermal conductivity.
- HFC-365 mfc 1,1,1,3,3-pentafluorobutane
- a blowing agent composition that benefits from the advantages of a LBA and/or LBC compound yet has less of the detrimental affects of the alcohol and/or carbonyl compound is desirable.
- a blowing agent composition that further comprises HFCs to reduce the thermal conductivity through a polymeric foam is also desirable, particularly if a mid-range low-boiling HFC partially replaces a low-range low-boiling HFC.
- Haldrofluorocarbon and “HFC” are interchangeable terms and refer to an organic compound containing hydrogen, carbon, and fluorine, the compound being substantially free of halogens other than fluorine.
- boiling point refers to the boiling point at one atmosphere pressure.
- Mid-range low-boiling hydrofluorocarbon “mid-range low-boiling HFC”
- MRLB HFC Magnetic-range low-boiling HFC
- Low-range low-boiling hydrofluorocarbon “low-range low-boiling HFC”
- LRLB HFC Low-range low-boiling HFC
- “Fresh” refers to within one month, preferably within one week, more preferably within one day, still more preferably within one hour, most preferably immediately after manufacture.
- LBA and/or LBC means “LBA, LBC, or LBA and LBC”.
- a polymeric foam or blowing agent composition that is “essentially free” of a specified component or components refers to a polymeric foam or blowing agent composition, respectively, that contains ten weight-percent (wt %) or less, preferably five wt % or less, more preferably one wt % or less, still more preferably 0.5 wt % or less, most preferably zero wt % of the specified component(s).
- the present invention is a blowing agent composition
- a blowing agent composition comprising: (a) at least one hydrofluorocarbon having a boiling point of 30° C. or higher and lower than about 120° C.; (b) at least one hydrofluorocarbon having a boiling point lower than 30° C.; and (c) at least one component selected from low-boiling alcohols and low-boiling carbonyl compounds.
- Embodiments of the first aspect include compositions that are essentially free of low-boiling carbonyl compounds and compositions that contain at least one of ethanol, acetone, and additional blowing agents.
- One preferred embodiment of the first aspect further comprises carbon dioxide at a concentration of less than 50 weight-percent of the composition.
- Another preferred embodiment of the first aspect comprises 1,1,1,3,3-pentafluorobutane, 1,1,1,2-tetrafluoroethane, ethanol, and carbon dioxide, wherein carbon dioxide is less than 50 weight-percent of the composition.
- the present invention is a process for preparing polymeric foam comprising the steps: (a) forming a foamable polymer composition from a polymer and the blowing agent composition of the first aspect; and (b) expanding said foamable polymer composition into a polymeric foam.
- the present invention is a polymeric foam that comprises: (a) a polymer; (b) a hydrofluorocarbon having a boiling point of 30° C. or higher and lower than about 120° C; (c) a hydrofluorocarbon having a boiling point lower than 30° C; and (d) at least one component selected from low-boiling alcohols and low-boiling carbonyl compounds.
- the present invention is a foamable polymer composition
- a foamable polymer composition comprising a polymer that has the blowing agent composition of the first aspect dispersed therein.
- blowing agent compositions of the present invention are particularly useful for preparing thermally insulating polymeric foam.
- This invention relates to a blowing agent composition
- a blowing agent composition comprising at least one MRLB HFC, at least one LRLB HFC, and at least one component selected from LBAs and LBCs.
- Suitable LBAs include aliphatic alcohols having from one to five carbons (C 1 -C 5 ) such as methanol, ethanol, n-propanol, and isopropanol. LBAs may or may not be anhydrous, but anhydrous (containing less than 1 weight-percent (wt %) water based on weight of alcohol) is preferred.
- the LBA is preferably ethanol or isopropanol, more preferably anhydrous ethanol.
- Suitable LBCs include any ketone or aldehyde that has a boiling point lower than about 120° C.
- Illustrative LBCs include acetone, 2-butanone, and acetaldehyde.
- the blowing agent composition may be free of LBA if a LBC is present, and may be free of LBC if a LBA is present, or may contain both a LBA and a LBC.
- the combined concentration of LBA and LBC, based on the blowing agent composition weight, is greater than zero wt %, preferably at least one wt %, more preferably at least five wt %, still more preferably at least 10 wt %; and typically 60 wt % or less, preferably 50 wt % or less, more preferably 40 wt % or less, still more preferably 20 wt % or less.
- LBA and/or LBC concentrations greater than 60 wt % tend to excessively plasticize the polymer, making processing difficult and result in inadequate polymeric foam thermal stability.
- Suitable MRLB HFCs include any HFC having a boiling point of 30° C. or higher and lower than about 120° C.
- suitable MRLB HFCs include aliphatic compounds such as HFC-365 mfc, 1-fluorobutane, nonafluorocyclopentane, perfluoro-2-methylbutane, 1-fluorohexane, perfluoro-2,3-dimethylbutane, perfluoro-1,2-dimethylcyclobutane, perfluorohexane, perfluoroisohexane, perfluorocyclohexane, perfluoroheptane, perfluoroethylcyclohexane, perfluoro-1,3-dimethyl cyclohexane, and perfluorooctane; as well as aromatic compounds such as fluorobenzene, 1,2-difluorobenzene; 1,4-difluorobenzene, 1,3-di
- HFC-365 mfc is particularly desirable due to its increasing availability and ease of use.
- Aromatic HFCs may also be attractive for preparing polymeric foams using an aromatic polymer if an enhanced compatibility between the HFC and polymer helps retain the HFC in the polymeric foam after formation.
- One advantage MRLB HFCs have over LRLB HFCS, in general, is that they typically remain longer within polymeric foam. HFC retention is attractive for slowing thermal conductivity increases and organic emissions associated with escaping HFC.
- MRLB HFCs are also easier to handle than LRLB HFCs because they are in a condensed phase at atmospheric pressure (760 mm mercury), therefore do not require liquefaction during the foaming process.
- the blowing agent compositions of the present invention comprise a MRLB HFC at a concentration relative to blowing agent composition weight of greater than zero wt %, generally ten wt % or more, more generally five wt % or more, still more generally three wt % or more; and generally 40 wt % or less, more generally 60 wt % or less, still more generally 80 wt % or less, and most generally 95 wt % or less. At a concentration greater than 95 wt %, MRLB HFC will excessively plasticize the polymer making foaming difficult.
- the blowing agent composition also comprises a LRLB HFC.
- the LRLB HFC typically acts both as-a blowing agent and as a thermal insulator in the polymeric foam.
- LRLB HFCs have low thermal conductivities, similar to the MRLB HFCs. Therefore, residual LRLB HFC in blown polymeric foam helps reduce the foam's thermal conductivity.
- LRLB HFC residuals generally occupy cell spaces while MRLB HFC residuals generally condense onto or into cell walls. Therefore, LRLB HFCs are generally more efficient at reducing polymeric foam thermal conductivity than MRLB HFCs.
- Suitable LRLB HFCs include methyl fluoride, difluoromethane (HFC-32), perfluoromethane, ethyl fluoride (HFC-161); 1,1-difluoroethane (HFC-152a); 1,1,1-trifluoroethane (HFC-143a); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1,2-tetrafluoroethane (HFC-134a); pentafluoroethane (HFC-125), perfluoroethane, 2,2-difluoropropane (HFC-272fb), 1,1,1-trifluoropropane (HFC-263fb), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,3,3-pentafluoropropane (HFC-245fa), and mixtures thereof.
- a preferred LRLB HFC is HFC-134a.
- the concentration of LRLB HFC in the blowing agent composition, relative to the total composition weight, is greater than zero wt %, often 10 wt % or more, more often 15 wt % or more, still more often 30 wt % or more, most preferably greater than 50 wt %.
- the upper concentration limit of LRLB HFC depends primarily on the solubility limit of the LRLB HFC in the polymer. Concentrations exceeding the solubility limit of a LRLB HFC in the polymer, in conjunction with the rest of the blowing agent composition, result in excessive nucleation during polymer expansion (blowing of the foam). A skilled artisan can determine without undue experimentation an upper limit for a LRLB HFC in a given blowing agent composition.
- the concentration of LRLB HFC is 95 wt % or less (relative to blowing agent composition weight), desirably 80 wt % or less, preferably 75 wt % or less, more preferably 60 wt % or less.
- the blowing agent composition preferably comprises at least one additional blowing agent, although additional blowing agents are not necessary. Additional blowing agents are useful for decreasing foam density. Proper choice of additional blowing agents may increase total moles of blowing agent without decreasing cell size, increasing density, and/or decreasing dimensional stability.
- Suitable additional blowing agents include inorganic and organic blowing agents as well as chemical blowing agents that decompose into inorganic and/or organic blowing agents.
- Suitable inorganic blowing agents include nitrogen, argon, water, air, and helium.
- Organic blowing agents include carbon dioxide (CO 2 ), ethers, aliphatic hydrocarbons having from one to nine carbons (C 1-9 ), fully and partially halogenated C 1-4 aliphatic hydrocarbons.
- Aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclobutane, and cyclopentane.
- Preferred additional blowing agents include water, CO 2 , isobutane, and cyclopentane. The most preferred additional blowing agent is CO 2 .
- the concentration of any individual additional blowing agent in a blowing agent composition is below the solubility limit of that blowing agent in the polymer at a process temperature (typically the glass transition temperature of the polymer) and in the presence of the entire blowing agent composition.
- additional blowing agents comprise 50 wt % or less, 30 wt % or less, even 10 wt % or less of the blowing agent composition.
- blowing agent composition The sum of CO 2 , MRLB HFC, LRLB HFC, LBA, LBC, and any additional blowing agents account for 100 wt % of the blowing agent composition.
- An example of a preferred blowing agent composition is 45-60 wt % HFC-134a, 25-40 wt % HFC-365 mfc, 10-20 wt % ethanol, and 1-10 wt % CO 2 .
- the present invention also relates to the use of a blowing agent composition comprising a LBA and/or LBC, a MRLB HFC, and a LRLB HFC to prepare foamable polymer compositions and polymeric foam.
- any conventional blown foam process is suitable for preparing blown polymeric foam using a blowing agent composition of this invention.
- polymeric foam is prepared by plasticizing a polymer, incorporating therein a blowing agent composition at an initial pressure to form a foamable composition, and then exposing the foamable composition to a foaming pressure that is lower than the initial pressure and allowing the foamable composition to expand into polymeric foam.
- a concentration, relative to weight parts of polymer resin of greater than zero parts-per-hundred (pph), preferably greater than 5 pph; and typically less than 25 pph, preferably less than 20 pph, and more preferably less than 15 pph to form a foamable polymer composition.
- pph parts-per-hundred
- Using greater than 25 pph blowing agent composition can produce foam with an undesirable density and cell size.
- a typical process for forming a foamable polymer composition includes: (1) plasticizing a polymer, typically by heating it to a processing temperature at or above its glass transition temperature or melting temperature, to form a plasticized polymer; and (2) adding a blowing agent composition to the plasticized polymer at an initial pressure to form a foamable polymer composition. Add components of the blowing agent composition individually or in any combination. Incorporate the blowing agent composition into the plasticized polymer by a batch or continuous process, using conventional equipment such as an extruder or mixer blender. The initial pressure is sufficient to prevent substantial expansion of the foamable composition and to generally disperse the blowing agent composition into the plasticized polymer. The initial pressure is usually, though not necessarily, greater than atmospheric pressure.
- Foam the foamable polymer composition by either reducing the pressure around the foamable composition to a foaming pressure or by transporting the foamable composition into a foaming zone at a foaming pressure.
- the foaming pressure is lower than the initial pressure and can be above or below atmospheric pressure, but is typically atmospheric pressure. Blowing agents in the blowing agent composition expand at the foaming pressure, expanding the foamable polymer composition into a polymeric foam.
- Cooling a heat plasticized foamable composition below the processing temperature prior to exposing the foamable composition to the foaming pressure is useful for optimizing foam properties. Cool the foamable composition in an extruder or other mixing device or in separate heat exchangers.
- the process comprises: 1) mixing a thermoplastic material and a blowing agent composition to form a foamable polymer composition; 2) extruding the foamable polymer composition into a holding zone maintained at a temperature and pressure that precludes foaming of the foamable polymer composition, the holding zone having a die defining an orifice opening into a zone of lower pressure and an openable gate closing the die orifice; 3) periodically opening the gate; 4) applying mechanical pressure substantially concurrently with (3) by means of a movable ram on the foamable polymer composition to eject it from the holding zone through the die orifice into the zone of lower pressure, and 5) allowing the ejected foamable polymer composition to expand to form a polymeric foam in the zone of lower pressure.
- Suitable polymers for use in the present invention include thermoplastic polymers.
- Suitable thermoplastic polymers include those selected from a group consisting of vinyl aromatic polymers such as polystyrene; rubber-modified vinyl aromatic polymers such as high impact polystyrenes (HIPS); vinyl aromatic copolymers such as styrene/acrylonitrile or styrene/butadiene copolymers; hydrogenated vinyl aromatic polymers and copolymers such as hydrogenated polystyrene and hydrogenated styrene/butadiene copolymers; alpha-olefin homopolymers such as low density polyethylene, high density polyethylene and polypropylene; linear low density polyethylene (an ethylene/octene-1 copolymer) and other copolymers of ethylene with a copolymerizable, mono-ethylenically unsaturated monomer such as an alpha-olefin having from 3 to 20 carbon atoms; copolymers of propylene with
- polystyrene resin examples include polyethylene terephthalate-glycol (PETG), phenol-formaldehyde resins, thermoplastic polyurethanes (TPUs), biodegradable polysaccharides such as starch, and polylactic acid polymers and copolymers.
- PET polyethylene terephthalate-glycol
- TPU thermoplastic polyurethanes
- biodegradable polysaccharides such as starch
- polylactic acid polymers and copolymers examples include polyvinyl chloride, polycarbonates, polyamides, polyimides, polyesters such as polyethylene terephthalate, polyester copolymers and modified polyesters such as polyethylene terephthalate-glycol (PETG), phenol-formaldehyde resins, thermoplastic polyurethanes (TPUs), biodegradable polysaccharides such as starch, and polylactic acid polymers and copolymers.
- the polymer is preferably polyethylene (PE), polystyrene (PS), polypropylene (PP), a blend of PS and an ethylene/styrene interpolymer (ESI), a blend of ESI and PE, a blend of ESI and PP, a blend of PS, PE and ESI or a blend of ESI with any one or more polyolefin or ethylene/alpha-olefin copolymers, terpolymers or interpolymers produced using a metallocene catalyst or a constrained geometry catalyst (such as The Dow Chemical Company's INSITETM catalysts, INSITE is a trademark of The Dow Chemical Company).
- PE polyethylene
- PS polystyrene
- PP polypropylene
- ESI ethylene/styrene interpolymer
- Additional additives such as those commonly used in preparing polymeric foam, can be included in the foamable composition.
- Additional additive may include pigments, viscosity modifiers, flame retardants, infrared blockers (e.g. carbon black and graphite), nucleating agents, permeation modifiers, and extrusion aids.
- nucleating agents is not necessary to prepare polymeric foam using blowing agent compositions of the present invention.
- the present invention further relates to polymeric foam comprising a polymer, a MRLB HFC, a LRLB HFC, and a LBA and/or LBC.
- a polymeric foam contains residuals of the blowing agent used in its manufacture.
- blowing agents tend to escape from polymeric foam and air tends to permeate into polymeric foam over time. Therefore, preferably characterize a polymeric foam within the timeframe set forth as “fresh”, most preferably immediately after manufacture, to ensure blowing agents have not escaped and air has not contaminated the foam.
- a polymeric foam may further contain additional blowing agents, such as CO 2 , when they are included in the blowing agent composition used to make the foam.
- One may identify the presence of blowing agent residuals using standard analytical techniques, such as gas chromatography.
- Polymeric foams of the present invention may take any physical configuration known in the art, such as sheet, rod, plank, or coalesced parallel strands and/or sheets.
- the foam is preferably a plank, more preferably a plank having a cross-section of 30 square centimeters (cm 2 ) or more and a cross-section thickness in a minor dimension of 0.25 inch (6.4 millimeters (mm)) or greater, more preferably 0.375 inch (9.5 mm)or greater, and still more preferably 0.5 inch (12.7 mm) or greater.
- a polymeric foam having a minor dimension of up to 8 inches (200 mm) is possible.
- the upper limit for the minor dimension is limited by foaming equipment limitations. Given large enough equipment, a minor dimension above 8 inches (200 mm) is conceivable.
- Polymeric foams of the present invention preferably have a density of 10 kilograms per cubic meter (kg/m 3 ) or greater, normally 25 kg/m 3 or greater and normally 100 kg/m 3 or less, more often 45 kg/m 3 or less. Polymeric foams having a density below 10 kg/m 3 generally lack a desired structural integrity. Polymeric foams of the present invention may have a density up to, but not including, that of a combination of the polymer and additives used in preparing the foam.
- Polymeric foam of the present invention can be open-celled (greater than 20 percent (%) open-celled) or close-celled (less than 20% open-celled), but foam that is less than 10% open-celled is preferable because it generally has a lower thermal conductivity. Determine percent open cell according to ASTM D2856-A.
- a polymeric foam of the present invention has a thermal conductivity 60 days after preparation, preferably 90 days after preparation (as determined according to ASTM method C- 518-98 using a sample temperature of 24° C.) of 35 milliwatt per meter-Kelvin (mW/m ⁇ K) or less, preferably 30 mW/m ⁇ K or less.
- Polymeric foams of the present invention have an average cell size greater than 0.05 millimeters (mm), preferably greater than 0.075 mm, more preferably greater than 0.1 mm, and less than 2 mm, preferably less than 1.2 mm. Determine average cell size using ATSM method D3576 with the following modifications: (1) image a foam using optical or electron microscopy rather than projecting the image on a screen; and (2) scribe a line of known length that spans greater than 15 cells rather than scribing a 30 mm line.
- PS F168 PS resin from The Dow Chemical Company, 168,000 weight-average molecular weight
- HBCD hexabromocyclododecane
- TSPP tetrasodiumpyrophosphate
- pph barium stearate 0.15 pph of blue concentrate (20 wt % copper phthalocyanine in PS by weight of concentrate)
- 0.2 pph linear low-density PE 2247a from The Dow Chemical Company
- blowing agent composition consisting of 73 wt % HFC-134a, 19 wt % anhydrous ethanol, and 8 wt % CO 2 (where wt % is relative to total blowing agent composition weight) to the molten mixture at an initial pressure of 14.5 megapascals (MPa) to form a foamable polymer composition.
- the total amount of blowing agent in Comp Ex A is 8.54 pph based on PS weight, or 0.12 moles per 100 grams of PS (mol/100 gPS).
- blowing agent composition consisting of 60 wt % HFC-134a, 16 wt % anhydrous ethanol, 8 wt % CO 2 , and 16 wt % HFC-365 mfc (where wt % is relative to total blowing agent composition weight) to the molten mixture at an initial pressure of 13.2 MPa to form a foamable polymer composition.
- the total amount of blowing agent in Ex 1 is 8.86 pph based on PS weight, or 0.12 mol/100 gPS.
- Table 1 contains foam density and thermal conductivity values as well as residual blowing agent concentration for both Comp Ex A and Ex 1. Measure foam density, after removing foam skins, according to ASTM method D- 1622-98. Measure thermal conductivity on Comp Ex A and Ex 1 immediately after manufacturing (fresh lambda) and 90 days after manufacturing (90 day lambda) according to ASTM method C 518-98 (at 24° C.).
- GC/MSD gas chromatography with mass selective detection
- Instrument settings are: column pressure (5 psi), sample wash (2), sample pumps (4), viscosity (0), solvent A (2), solvent B (2), purge B (off), detector temperature (260° C.), injector temperature (260° C.), oven equilibration (0.50 minutes), oven program (50° C. for 2 minutes then ramp 15° C./minute to 65° C. and hold for 2 minutes).
- Detector settings are: solvent delay (0), EM absolute (1360), low mass (35), high mass (100), EMV offset (0), Sampling (2), scan/second (10.2), voltage (1360), threshold (150). Monitor ion mass 83 for HFC-134a, ion mass 65 for HFC-365 mfc, and ion mass 43 for-ethanol.
- This method does not detect (ND) CO 2 , so no CO 2 values are in Table 1. Measure residual blowing agent concentration on 125-130 days after manufacture. Essentially all CO 2 is expected to escape from the foams prior to measuring residual blowing agent concentrations.
- Foam density is in pounds-per-cubic foot (pcf) and kilograms-per-cubic meter (kg/m 3 ).
- the pph values in Table 1 are relative to PS resin weight.
- Thermal conductivities are in milliWatt per meter-Kelvin (mW/m*K).
- Ex 1 A comparison of Ex 1 to Comp Ex A illustrates that thermal conductivity is not significantly affected in a PS foam by reducing ethanol and HFC-134a and including HFC-365 mfc in a blowing agent composition used to prepare the PS foam.
- Ex 1 demonstrates more residual blowing agent than Comp Ex B, illustrating an improved retention of blowing agent composition and therefore less blowing agent emissions with the HFC-365 mfc blowing agent formulation over the blowing agent formulation free of HFC-365 mfc.
- HFC-365 mfc remains in a PS foam longer than HFC-134a. 83% of the HFC-365 mfc in the blowing agent composition remains in the foam after 125 days, as compared to 71% of the HFC-134a.
- Comp Ex B and Ex 2-6 in a manner similar to Comp Ex A and Ex 1 except use blowing agent compositions and blowing agent addition pressures as in Table 2.
- Comp Ex A is free from HFC-365 mfc and Ex 2-6 include HFC-365 mfc as a partial replacement for HFC-134a, ethanol, and water.
- Blowing agent concentrations are in wt % relative to PS weight (values in parentheses are relative to total blowing agent weight). Initial pressure is in MPa. Total blowing agent concentration is in pph relative to PS resin weight and in moles per hundred grams of PS (mol/100 gPS).
- Foam density is in kg/m 3 (values in parentheses are pcf). Concentrations are in wt % relative to PS resin, thermal conductivities are in mW/m*K. Total blowing agent is in pph relative to PS resin weight.
- Ex 2-6 illustrate that partially replacing HFC-134a, ethanol, CO 2 , and water with HFC-365 mfc in a blowing agent composition for polystyrene foam can both a lower 90 day lambda value and increase blowing agent composition remaining in the foam.
- XZ40 PS resin is a blend having a weight average molecular weight (M w ) of 151,000; a polydispersity (M w /M n ) of 3.1; and a melt flow index (MFI) of 33 grams per 10 minutes (g/10 min). Determine MFI using ASTM method D-1238 (190° C., 5 kg load).
- a blowing agent composition (see below) into the polymer melt at a pressure of 164 bar (16.4 megaPascals (MPa)) and mix to form a foamable polymer composition. Cool to 125° C. and extrude the foamable polymer composition through slit die (50 mm wide with a 0.8 mm opening) to atmospheric pressure to form a 30 mm thick and 180 mm wide polymeric foam.
- blowing agent composition in wt % relative to PS resin weight and, in parentheses, relative to total blowing agent weight
- resulting foam parameters for Comp Ex C and Ex 7 are in Table 4.
- Ex 7 illustrates that partially replacing CO 2 , ethanol, and an LRLB HFC (HFC-245 fa) with an MRLB HFC (HFC-365 mfc) while keeping the total moles of blowing agent constant can reduce a foam's thermal conductivity 90 days after manufacturing.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US09/999,277 US6476080B2 (en) | 2000-12-21 | 2001-11-29 | Blowing agent compositions containing hydrofluorocarbons and a low-boiling alcohol and/or low-boiling carbonyl compound |
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US25748300P | 2000-12-21 | 2000-12-21 | |
US09/999,277 US6476080B2 (en) | 2000-12-21 | 2001-11-29 | Blowing agent compositions containing hydrofluorocarbons and a low-boiling alcohol and/or low-boiling carbonyl compound |
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US20020132868A1 US20020132868A1 (en) | 2002-09-19 |
US6476080B2 true US6476080B2 (en) | 2002-11-05 |
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US09/999,277 Expired - Lifetime US6476080B2 (en) | 2000-12-21 | 2001-11-29 | Blowing agent compositions containing hydrofluorocarbons and a low-boiling alcohol and/or low-boiling carbonyl compound |
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US (1) | US6476080B2 (zh) |
EP (1) | EP1353981B1 (zh) |
JP (1) | JP3934552B2 (zh) |
KR (1) | KR20030064853A (zh) |
CN (1) | CN1204173C (zh) |
AT (1) | ATE371697T1 (zh) |
AU (1) | AU2002219980A1 (zh) |
CA (1) | CA2431694A1 (zh) |
DE (1) | DE60130258T2 (zh) |
DK (1) | DK1353981T3 (zh) |
ES (1) | ES2290097T3 (zh) |
HU (1) | HUP0400742A3 (zh) |
MX (1) | MX234823B (zh) |
NO (1) | NO20032832L (zh) |
RU (1) | RU2275395C2 (zh) |
WO (1) | WO2002051919A2 (zh) |
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US20020198274A1 (en) * | 2001-06-01 | 2002-12-26 | Bogdan Mary C. | Compositions of hydrofluorocarbons and methanol |
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US20060047009A1 (en) * | 2004-09-03 | 2006-03-02 | Handa Yash P | Insulating thermoplastic foams made with methyl formate-based blowing agents |
US20060052466A1 (en) * | 2004-09-03 | 2006-03-09 | Handa Yash P | Expanded and extruded thermoplastic foams made with methyl formate-based blowing agents |
US20060052464A1 (en) * | 2004-09-03 | 2006-03-09 | Handa Yash P | Thermoplastic foams made with methyl formate-based blowing agents |
US20060052465A1 (en) * | 2004-09-03 | 2006-03-09 | Handa Yash P | Thermoplastic foams made with methyl formate-based blowing agents |
US20060073308A1 (en) * | 2004-09-23 | 2006-04-06 | Royal Group Technologies Limited | Method of partially engraving foamed plastic extrusions and extrusions so engraved |
WO2007101034A2 (en) | 2006-02-22 | 2007-09-07 | Pactiv Corporation | Polyolefin foams made with methyl formate-based blowing agents |
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US20090203808A1 (en) * | 2008-02-12 | 2009-08-13 | Nova Chemicals Inc. | Expandable particulate polymer composition |
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EP1548051A1 (en) * | 2003-11-26 | 2005-06-29 | SOLVAY (Société Anonyme) | Replacement of hydrochlorofluorocarbons for polymer foam manufacture |
JP2006096903A (ja) * | 2004-09-30 | 2006-04-13 | Kanebo Ltd | ポリ乳酸系樹脂発泡体 |
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Cited By (34)
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US20020198274A1 (en) * | 2001-06-01 | 2002-12-26 | Bogdan Mary C. | Compositions of hydrofluorocarbons and methanol |
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US20040249010A1 (en) * | 2003-06-04 | 2004-12-09 | Honeywell International, Inc. | Azeotrope-like compositons of pentafluoropropane, chloropropane and methanol |
US20060052465A1 (en) * | 2004-09-03 | 2006-03-09 | Handa Yash P | Thermoplastic foams made with methyl formate-based blowing agents |
US20060052466A1 (en) * | 2004-09-03 | 2006-03-09 | Handa Yash P | Expanded and extruded thermoplastic foams made with methyl formate-based blowing agents |
US20060052464A1 (en) * | 2004-09-03 | 2006-03-09 | Handa Yash P | Thermoplastic foams made with methyl formate-based blowing agents |
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CA2431694A1 (en) | 2002-07-04 |
NO20032832D0 (no) | 2003-06-20 |
ATE371697T1 (de) | 2007-09-15 |
US20020132868A1 (en) | 2002-09-19 |
MXPA03005693A (es) | 2004-04-21 |
HUP0400742A2 (hu) | 2004-07-28 |
NO20032832L (no) | 2003-08-20 |
JP3934552B2 (ja) | 2007-06-20 |
MX234823B (es) | 2006-03-13 |
JP2004516375A (ja) | 2004-06-03 |
KR20030064853A (ko) | 2003-08-02 |
CN1204173C (zh) | 2005-06-01 |
EP1353981B1 (en) | 2007-08-29 |
WO2002051919A2 (en) | 2002-07-04 |
EP1353981A2 (en) | 2003-10-22 |
CN1483059A (zh) | 2004-03-17 |
RU2275395C2 (ru) | 2006-04-27 |
AU2002219980A8 (en) | 2005-10-13 |
ES2290097T3 (es) | 2008-02-16 |
DE60130258D1 (de) | 2007-10-11 |
WO2002051919A3 (en) | 2003-04-10 |
HUP0400742A3 (en) | 2008-03-28 |
DK1353981T3 (da) | 2008-01-21 |
DE60130258T2 (de) | 2008-05-21 |
AU2002219980A1 (en) | 2002-07-08 |
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